Seton Hall University Dissertations and Theses (ETDs)

Reversed phase high performance liquid chromatography, chosen because of its ability to collect many data points over a long period of time with minimal involvement, was used to separate pentaamminenitritocobalt(III) chloride and pentaamminenitrocobalt(III) chloride. Pentaamminenitritocobalt(III) chloride was prepared, made into a concentrated solution, divided into aliquots and allowed to isomerize to pentaamminenitrocobalt(III) chloride over a period of twelve to eighteen hours. An injection was made approximately every forty-five minutes. The samples were analyzed at three wavelengths, 254 nm, 460 nm and 490 nm. The absorbance was collected and was used to determine the kinetics of the ...

All Theses

One of the thrust areas of our research deals with exploratory synthesis of new inorganic-organic hybrid materials for energy storage. It is well-known that relevant to the research described later in this thesis, inorganic-organic hybrid solids studied thus far are largely made of coordination complexes where the organic molecules are acting like a ligand to coordinate around metal cations. In this research, we will employ polyoxometalate (POM) anions as an inorganic building block to replace otherwise oppositely charged metal cations in hopes to synthesize extended hybrid frameworks with rich redox chemistry. POM clusters are made of aggregates of transition-metal (TM ...

Undergraduate Honors Theses

Twenty-one novel complexes of copper(II) thiocyanate pyridine were synthesized in methanol from the source material Cu(NO­3)2•2.5H2O and a diverse series of substituted pyridines (XPy). These complexes typically formed according to the formula trans-[Cu(NCS)2(XPy)2], with square-planar geometries that exhibited thiocyanate bridging via long Cu–S bonds. The length of this long bridging bond appears to loosely correlate to the substitution position of the pyridine ligand used, and resulted in square planar molecules forming edge-sharing chain networks of Jahn-Teller distorted octahedra. Several other structural types were also observed, resulting ...

Synthesis And Applications Of Lanthanide Sulfides And Oxides, Christopher Marin

This dissertation focuses on two of the key fields where lanthanides find ready application: as optically active materials with a focus on the lanthanide sulfides, and as catalytic materials with a focus on cerium oxide.

The lanthanide sulfides have attracted considerable interest for their potential as solar energy conversion materials, pigments, infrared window materials, and phosphor host media. However, applications of these materials remain limited due to their synthetic difficulty along with their not well understood properties compounded by both their difficulty in manufacturing as well as in simulating largely due to the need to take into account f-shell electrons ...

Honors Thesis

Reactive ligand platforms containing trisubstituted boranes have been effective in promoting new types of small molecule reactivity and catalysis with transition metals. Our project is aimed at developing triaminoborane-bridged diphosphines that participate in cooperative ligand-centered reactivity while bound to transitions metals. Here we present a density functional theory (DFT) mechanistic study on a series of ligand centered reactions at a boron center on a metal complex, PhTBDPhosMCl2 (M = Ni or Pd and TBDPhos = 1,8,10,9-triazaboradecalin). Our work focuses specifically on the nickel complexes. PhTBDPhosNiCl2 can react with several molecules to produce trans H-X addition ...

Honors Theses

In this project, the vibrational characteristics/vibrational modes are explored via Raman Spectroscopy for thiolated-gold nanoparticles. This class of compounds is also known as gold nanoparticles (AuNPs). They remain of great interest in research areas such as catalysis, gold dependent nanoelectronics, drug delivery, and sensing, due to their unique size-dependent optical, chiroptical, and electronic properties. Vibrational spectroscopy of thiolated gold nanoparticles are oftentimes considered nontrivial as the compounds strongly absorb light in the visible region of the electromagnetic spectrum, are generally considered weak scatterers, and give off large amounts of fluorescence. This combined with their black appearance, susceptibility to localized ...

The Synthesis Of A Mepeg-Based Hydroxide Conducting Electrolyte And The Optimization Of The Mepeg-Tosylation Reaction, Andrew Ladner

Honors Theses

As society is becoming increasingly aware of the effects of climate change and the ever-looming threat of a fuel shortage, exploring green and renewable alternative energy production, such as fuel cells, is paramount. This project investigates the synthesis of a polyethylene glycol monomethyl ether (MePEGn) based polymer as well as the optimization of the MePEG Tosylation reaction. The MePEG explored contains seven polymerized ethoxy groups (MePEG7). The MePEG7 polymer was modified by substituting a positively-charged trimethylamine group in the place of the alcohol functional group at the end of the PEG chain. The reason for this substitution ...

Honors Thesis

Upconversion (UC), is a phenomenon that occurs when low-energy excitation (usually near-infrared (NIR)) results in higher-energy emission. Upconversion nanoparticles (UCNPs) are particles less than 100 nm in size that are synthesized using rare earth metals such as Yb, Er, Tm, and Y. UCNPs have important applications in a variety of fields, including bio-imaging, security printing, and latent fingerprint development. Traditional methods for latent fingerprint development such as fluorescent powder dusting have several drawbacks including low contrast, high background interference, and autofluorescence. NIR-to-NIR UCNPs are composed of NaYF4: Yb, Tm and emit 800 nm light under 980 nm excitation due ...

Optimization Of The Mechanochemical Synthesis Of Several Distinct Compounds., Joseph Ryan Williams

Honors College Theses

Mechanochemical synthesis, as used in this work, is the mechanical milling of reagents to drive reaction. It is often considered a greener alternative to traditional solution-based methods of synthesis. This work will describe the mechanochemical synthesis of furan-2-yl(pyrrolidin-1-yl)methanethione and N-hexadecylfuran-2-carbothioamide, the optimization of the mechanochemical synthesis of 1,3-dibenzylbenzimidazolium bromide as well as the kinetics of this reaction, and finally the ongoing development of the mechanochemical synthesis of N,N′-dioctyl-2,2′-bipyridine-4,4′-dicarboxamide.

This work studied both the traditional method and mechanochemical method for synthesis of furan-2-yl(pyrrolidin-1-yl)methanethione, as well as the mechanochemical method ...

Electronic Thesis and Dissertation Repository

The synthesis of heterometallic chalcogenide molecules requires the continued investigation into the appropriate reagents necessary to introduce metal – chalcogen bonds in a controlled fashion. Trimethylsilyl metallochalcogenolates (MESiMe3) act as synthons introducing “ME–“ in solution upon reacting with an appropriate ternary metal reagent, MX (X= halide, acetate, etc.). Recent work makes use of N–heterocyclic carbenes (NHCs) as a class of ancillary ligand that can stabilize these reagents and the heterometallic chalcogenide molecules obtained with them. Building on previous work, this thesis describes the synthesis of group 11 trimethylsilyl metallochalcogenolates stabilized by bis–1,3–tritylimidazole–2–ylidene (abbreviated ITr ...

GREAT Day

Because of humans’ heavy impact on nature with industrialization and resource extraction, biomimetics, also known as biomimicry, is a study that has emerged. Biomimetics utilizes observations from nature to comprehend the principles of underlying mechanisms and apply concepts that may benefit science, medicine, engineering and the like. An area of biochemistry we are applying this to is the lactate racemase enzyme.This metalloenzyme is found in many prokaryotic organisms and catalyzes the interconversion between the two optical isomers of lactic acid. The structure of this enzyme consists of a square-planar nickel (II) ion coordinated by a histidine residue and a ...

19th Annual Celebration of Undergraduate Research and Creative Activity (2020)

Improving student success in chemistry requires faculty change, but change is hard. The Interactive Online Network of Inorganic Chemists (IONiC) is a community of practice (CoP) that offers teaching resources for inorganic chemistry faculty. We are studying the ways in which CoPs can promote faculty change. IONiC is supporting twenty inorganic chemistry faculty in implementing effective teaching methods into their foundation-level inorganic chemistry courses. In order to better understand how faculty make decisions about teaching, these faculty were interviewed about their teaching beliefs, approaches, and dissatisfactions. The interview data were coded via thematic content analysis and have shown that inorganic ...

Design Of Pigments For Use In “Cool” Coatings, Tyler Laughorn

Williams Honors College, Honors Research Projects

This project was focused on the development and testing of several novel pigments that exhibit high NIR-reflectance and therefore show potential for use in “cool” coatings. A “cool” coating will reflect more solar radiation than other standard coatings, and so a coated structure would require less energy to keep cool. Four sets of pigments were synthesized: Co1-xMgxCr2O4 (teal), Co0.25Mg0.75Cr2-yAlyO4 (blue), Ti1-x-yNixSbyO2 (yellow), and Cr2-xFexO3 (black). NIR and TSR values were ...

Greener Synthesis Of Chlorophosphazenes, Andrew Mcgee

Williams Honors College, Honors Research Projects

This project will attempt to synthesize chlorophosphazene molecules in the absence of solvents by using mechanochemical techniques in order to create a more environmentally friendly synthesis route. In this pursuit, various parameters will be changed including the milling ball to reagent ratios, the molar ratios of the reactants, and the addition of different catalysts. The products of each reaction will be characterized in order to determine success. This work builds upon existing efforts to utilize mechanochemical techniques in main group chemistry. The output of this project will be a report in ACS style and a poster to be presented for ...

Synthesis And Reactivity Of A New Platinum(Ii) Complex, Maria Lew

Scripps Senior Theses

Alkanes are some of the most abundant organic molecules, yet currently there are no efficient ways of directly converting them to more functional molecules. One viable method of direct functionalization is C–H bond activation by transition metal catalysts. The focus of this research has been the synthesis of a new Pt(II) pincer complex to be used in mechanistic investigations of C–H activation, as well as the beginnings of those investigations. The complex [NNON]PtMe was successfully synthesized. Reactions with various acids indicated that [NNON]PtMe is capable of reductively eliminating methane after addition ...

Chemistry Theses and Dissertations

In modern organic chemistry, hypervalent (HV) iodine(III) compounds are frequently used as oxidizing agents but application of λ3-iodanes in polymer and material chemistry is still underexplored. This dissertation describes the preparation of dynamic and self-healing materials by employing ligand exchange reactions involving HV iodine(III) compounds of the type ArIL2 (Ar = Aryl, L = ligand, e.g., carboxylate or (pseudo)halide). These compounds can undergo ligand exchange reactions in presence of nucleophiles (Nu-) to form ArINu2. Diacetoxyiodo benzene was successfully employed as a crosslinker to prepare dynamic and self-healing gels derived from carboxylate-containing polymers. Furthermore, advantage ...

Electronic Theses and Dissertations

The present thesis deals with the synthesis and study of the physico-chemical properties of perovskite based oxide materials. Several novel oxygen deficient perovskites (ODP) have been synthesized by conventional solid state synthesis method. The novel compounds are CaSrFe2O6-δ, CaSrFeCoO6-δ, Ca2Fe1.5Ga0.5O5, CaSrFeGaO5 and BaSrFe2O5. Their magnetic, charge transport and electrocatalytic properties have been studied. Structural effect on electrical conductivity, magnetic and electrocatalytic properties have been studied in some series of ODPs. CaSrFe2O6-δ, CaSrFeCoO6-δ, Ca2Fe1.5Ga0 ...

Self-Assembly Of 2d And 3d Metallo-Supramolecules With Increasing Complexity, Bo Song

Graduate Theses and Dissertations

Synthetic organic chemistry played a crucial role in the construction of molecules through the formation and dissociation of covalent bonds. However, the laborious synthetic procedures as well as the low yield after multiple steps have restricted the pursuit of complicated giant molecules with high efficiency. Being complementary to organic synthesis, self-assembly provided an alternative route to achieving the giant architectures using weak non-covalent interactions in high efficiency, which is in analog to natural systems such as DNA, peptide, and protein. Among the various interactions, coordination has shown unique advantages in terms of directionality, reversibility and strength. Serving as a bottom-up ...

Georgia Undergraduate Research Conference (GURC)

Metal flux reactions use a low-melting metal present in excess as a solvent to allow reactions to occur at low enough temperatures to obtain kinetic and metastable products as well as production of crystals due to the liquid medium. It was of interest to use metal flux to synthesize sulfides or selenides that were semiconductors with a band gap between 1-2 eV. In this project, bismuth or an equimolar mixture of indium and bismuth were used as fluxes for the synthesis of Cu3BiS3 and InSe respectively. Production of these compounds was confirmed with powder X-ray diffraction (PXRD ...

Doctoral Dissertations

Anion exchange membranes (AEMs) are notorious for having both low alkaline stability and poor ion conductivity in fuel cell operation conditions, with solutions to these two challenges often being developed independent of each other. The chemical instability of an AEM is viewed through degradation of the polymer backbone and the cationic species and improving a material’s stability is approached by altering the polymer backbone, the cation, or both. On the other hand, poor ion conductivity is typically addressed by modifying bulk membrane properties such as increasing the ion exchange capacity (IEC), changing the morphology, or increasing the water uptake ...

Progress Toward Durable Icephobic Materials, Matthew J. Coady

Electronic Thesis and Dissertation Repository

Ice accumulation is a major engineering challenge in many fields including aerospace, power generation, transportation, and infrastructure. A variety of solutions are being researched to address this challenge. Perhaps the most promising method of combating ice accumulation is by applying coatings with low values of interfacial ice adhesion strength, τice. Icephobic materials are those with ice adhesion below 100 kPa, and it has been shown that passive delamination can occur on surfaces with τice below 20 kPa. While various low adhesion surfaces have been prepared, durability concerns pervade applications where surfaces experience repeated icing or freeze-thaw cycles, mechanical ...

Electronic Thesis and Dissertation Repository

Synthesis of zinc phosphide (Zn3P2) nanoparticles is an emerging topic of investigation as Zn3P2 is a candidate material for the next generation solar cells. Despite the early discovery of its favorable electronic properties that are well-suited for photovoltaic applications, a major focus of synthetic strategy was with vapor/chemical deposition methods. Solution methods with greater control over size, crystal structure and composition at a lower production cost, has been underdeveloped in comparison. In this context, this thesis describes the synthesis, characterization and reactivity of zinc phosphido clusters: [Zn2(μ-PPh2)2(PPh2 ...

Theses and Dissertations

Platinum-based drugs have over the years been administered in the treatment of tumours.

Unfortunately, platinum resistance and the severe side effects associated with the treatments has necessitated the research for new anti-cancer drugs. Ruthenium(II) and Ruthenium(III) complexes have shown promise as useful alternative anticancer agents. The lead candidates include the Ru(II) complex RAPTA-C, a ruthenium(II)-arene complex [Ru(η6-p-cymene)Cl2(1,3,5-triaza-7-phosphaadamantane)] and the Ru(III) complex NAMI-A [imidazoleH][trans-Ru(imidazole) (dimethyl sulfoxide)Cl4]. Both compounds have shown potent cytotoxic activity in several primary human tumor models. Unfortunately, NAMI-A could not advance in clinical evaluations ...